On the chemical bonding effects in the Raman response: Benzenethiol adsorbed on silver clusters

We study the effects of chemical bonding on Raman scattering from benzenethiol chemisorbed on silver clusters using time-dependent density functional theory (TDDFT). Raman scattering cross sections are computed using a formalism that employs analytical derivatives of frequency-dependent electronic polarizabilities, which treats both off-resonant and resonant enhancement within the same scheme. In the off-resonant regime, Raman scattering into molecular vibrational modes is enhanced by one order of magnitude and shows pronounced dependence on the orientation and the local symmetry of the molecule. Additional strong enhancement of the order of $10^2$ arises from resonant transitions to mixed metal--molecular electronic states. The Raman enhancement is analyzed using Raman excitation profiles (REPs) for the range of excitation energies $1.6-3.0$ eV, in which isolated benzenethiol does not have electronic transitions. The computed vibrational frequency shifts and relative Raman scattering cross sections of the metal--molecular complexes are in good agreement with experimental data on surface enhanced Raman scattering (SERS) for benzenethiol adsorbed on silver surfaces. Characterization and understanding of these effects, associated with chemical enhancement mechanism, may be used to improve the detection sensitivity in molecular Raman scattering.Comment: 25 pages, 14 figures. Phys. Chem. Chem. Phys. in pres

Latitude dictates plant diversity effects on instream decomposition

Running waters contribute substantially to global carbon fluxes through decomposition of terrestrial plant litter by aquatic microorganisms and detritivores. Diversity of this litter may influence instream decomposition globally in ways that are not yet understood. We investigated latitudinal differences in decomposition of litter mixtures of low and high functional diversity in 40 streams on 6 continents and spanning 113 degrees of latitude. Despite important variability in our dataset, we found latitudinal differences in the effect of litter functional diversity on decomposition, which we explained as evolutionary adaptations of litter-consuming detritivores to resource availability. Specifically, a balanced diet effect appears to operate at lower latitudes versus a resource concentration effect at higher latitudes. The latitudinal pattern indicates that loss of plant functional diversity will have different consequences on carbon fluxes across the globe, with greater repercussions likely at low latitudes

The University, Neighborhood Revitalization, and Civic Engagement: Toward Civic Engagement 3.0

This essay analyzes and syntheses key theories and concepts on neighborhood change from the literature on anchor institutions, university engagement, gentrification, neighborhood effects, Cold War, Black liberation studies, urban political economy, and city building. To deepen understanding of the Columbia University experience, we complemented the literature analysis with an examination of the New York Times and Amsterdam newspapers from 1950 to 1970. The study argues that higher education’s approach to neighborhood revitalization during the urban renewal age, as well as in the post-1990 period, produced undesirable results and failed to spawn either social transformation or build the neighborly community espoused by Lee Benson and Ira Harkavy. The essay explains the reasons why and concludes with a section on a more robust strategy higher education can pursue in the quest to bring about desirable change in the university neighborhood